EP0133938A2 - Process for preparing amines - Google Patents
Process for preparing amines Download PDFInfo
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- EP0133938A2 EP0133938A2 EP84108454A EP84108454A EP0133938A2 EP 0133938 A2 EP0133938 A2 EP 0133938A2 EP 84108454 A EP84108454 A EP 84108454A EP 84108454 A EP84108454 A EP 84108454A EP 0133938 A2 EP0133938 A2 EP 0133938A2
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- Prior art keywords
- catalyst
- ammonia
- amine
- zeolite
- olefin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the invention relates to a process for the preparation of amines by addition of ammonia or analogous amines to olefins.
- the process according to the invention is characterized in that a high selectivity of the desired reaction product is achieved even with a low excess of ammonia or amine and the dimerization and / or oligomerization of the olefin used is avoided.
- One embodiment of this process consists in that ammonia and / or amines are mixed together with olefins in a molar ratio of 1: 1 to 5: 1 and fed to a fixed bed or fluidized bed reactor and at a pressure of 40 to 700 bar, in particular 200 to 300 bar and a temperature of 80 to 400 ° C, in particular from 250 to 350 ° C in the gas phase or in the supercritical state.
- the reaction in the liquid phase is carried out at a pressure of 40 to 80 bar and a temperature of 60 ° C to 120 ° C in a stirred tank, a solid / liquid fluidized bed or a flow tube.
- the desired product is obtained from the reaction discharge using known methods, for example distillation or extraction, and If necessary, brought to the desired purity by means of further separation operations.
- the unreacted input materials are returned to the reactor.
- the location of the optimum temperature with regard to conversion and selectivity depends on the constitution of the olefin, the amine used and the catalyst and is usually in the range from 250 ° C. to 350 ° C.
- the dwell time depends on the starting materials and is expediently in the range between fractions of a second and a few minutes.
- Borosilicate or borogermanate zeolites of the pentasil type are used as catalysts for the amination of olefins.
- Suitable borosilicate zeolites or borogermanate zeolites are synthesized at 90 to 170 ° C under autogenous pressure by using a boron compound, for example H 3 B0 3 with a silicon compound or a germanium compound, preferably highly disperse silicon dioxide and germanium oxide in aqueous amine solution, especially in 1,6-hexanediamine - or 1,3-propanediamine or triethylenetetramine solution with and without addition of alkali or alkaline earth metal to react.
- a boron compound for example H 3 B0 3 with a silicon compound or a germanium compound, preferably highly disperse silicon dioxide and germanium oxide in aqueous amine solution, especially in 1,6-hexanediamine - or 1,3-propanediamine or triethylenetetramine solution with and without addition of alkali or alkaline earth metal to react.
- Such borosilicate zeolites or borogermanate zeolites can also be prepared if the reaction is carried out in ethereal solution, e.g. Diethylene glycol dimethyl ether or in alcoholic solution, e.g. Performs methanol or 1,4-butanediol.
- ethereal solution e.g. Diethylene glycol dimethyl ether
- alcoholic solution e.g. Performs methanol or 1,4-butanediol.
- the borosilicate zeolites and borogermanate zeolites thus produced can be isolated after their isolation, drying at 100 to 160 ° C, preferably at about 110 ° C and calcination at 450 to 550 ° C, preferably at about 500 ° C, with a binder in a ratio of 90:10 to 40:60 wt .-% to form strands or tablets.
- Various aluminum oxides preferably boehmite, amorphous aluminosilicates with an SiO 2 / Al 2 O 3 ratio of 25:75 to 95: 5, silicon dioxide, preferably highly disperse Si0 2 , mixtures of highly disperse Si0 2 and highly disperse A1 2 0 3 are suitable as binders , highly disperse TiO 2 and clay.
- the extrudates or compacts are expediently dried at 110 ° C./16 h and calcined at 500 ° C./16 h.
- a special embodiment consists in that the isolated borosillate and / or borogermantzeolite is deformed immediately after drying and is subjected to a caleination for the first time after the deformation.
- the catalysts can be regenerated in a simple manner by burning off the coke deposit with air or with an air / N 2 mixture at 400 ° C. to 550 ° C., preferably at about 500 ° C. . This gives you back your initial activity.
- a modification of the catalysts is that the undeformed or the deformed zeolites with alkali metals such as Na and K, alkaline earth metals such as Ca, Mg, earth metals such as Tl, transition metals such as Mn, Fe, Mo, Cu, Zn and rare earth metals such as La, _Ce ion noise or doping.
- alkali metals such as Na and K
- alkaline earth metals such as Ca, Mg
- earth metals such as Tl
- transition metals such as Mn, Fe, Mo, Cu, Zn
- rare earth metals such as La, _Ce ion noise or doping.
- an advantageous embodiment is that the deformed pentasil zeolites are placed in a flow tube and at 20 to 100 ° C, e.g. a halide or a nitrate of the metals described above passes over it.
- ion exchange can e.g. on the hydrogen, ammonium and alkali form of the zeolites.
- Another way of applying metal to the zeolites is to use the zeolitic material, e.g. impregnated with a halide, a nitrate or an oxide of the metals described above in aqueous or alcoholic solution.
- Both ion exchange and impregnation can be followed by drying or, alternatively, repeated calcination.
- post-treatment with hydrogen and / or with water vapor can be advantageous.
- Another possibility for modification consists in subjecting the zeolitic material - deformed or undeformed - to treatment with acids such as hydrochloric, hydrofluoric and phosphoric acids.
- a special embodiment consists in treating the zeolitic powder under reflux with hydrofluoric acid 0.001 n to 2 n, preferably 0.05 to 0.5 n, for 1 to 3 hours before it is shaped. After filtering off and washing out, it is dried at 100 to 160 ° C. and calcined at 400 to 550 ° C.
- Another special embodiment is an HCl treatment of the zeolites after they have been deformed with a binder.
- the zeolite is treated for 1 to 3 hours between 60 and 80 ° C with a 3 to 25%, in particular with a 12 to 20% hydrochloric acid, then washed out, dried at 100 to 160 ° C and at 400 to 550 ° C calcined.
- the zeolite which is present in the H form or another ammonium form and deformed with binder, is continuously at 60 to 80 ° C. with 10 to 25%, preferably 20%, NH 4 Cl solution in a weight-based zeolite / ammonium chloride solution exchanged by 1:15 and then dried at 100 to 120 ° C.
- the catalysts can be used as 2 mm to 4 mm strands, as tablets with 3 to 5 mm diameter or as fluidized material with a size of 0.1 to 0.8 mm or as split with 0.5-1 mm diameter for the amination of the Use olefins.
- Catalyst A is in a hydrothermal synthesis from 64 g Si0 2 (highly disperse silica) 12.2 g H 3 BO 3 , 800 g of an aqueous 1,6-hexanediamine solution (mixture 50:50 wt .-%) at 170 ° C produced under autogenous pressure in a stirred autoclave. After filtering off and washing out, the crystalline reaction product is dried at 110 ° C./24 h and at 500 ° C./24 h calcined. A pentasil type borosilicate zeolite is obtained which contains 94.2% by weight of SiO 2 and 2.32% by weight of B 2 0 3 .
- 2 mm strands are produced from this zeolite by shaping with boehmite in a weight ratio of 60:40, which are dried at 110 ° C./16 h and calcined at 500 ° C./24 h.
- Catalyst B is prepared by treating 50 g of the borosilicate zeolite described above with 140 ml of O, lN HF under reflux for 1 h. After filtration and washing with water, the mixture is dried at 110 ° C./16 h and calcined at 500 ° C./5 h. This product is extruded with boehmite in a ratio of 60:40, dried at 110 ° C./16 h and calcined at 500 ° C./16 h.
- Catalyst C is obtained by carrying out an ion exchange with a Na compound at RT on catalyst A, so that the catalyst, after washing out with water and drying at 110 ° C./16 h, has a Na content of 0.32% by weight. having.
- each of the catalysts A, B or C described above are placed in a 0.3 l stirred autoclave and, after sealing, the olefins and ammonia or amines are pressed on.
- the amount of product used is such that the desired pressure is reached as the intrinsic pressure of the reactants at the selected reaction temperature.
- the molar ratio of ammonia / amine to olefin is varied from 1: 1 to 5: 1, the reaction time to 30 min. fixed.
- a high-pressure reactor with a length of 2 m and an inner diameter of 24 mm is used, which is heated by an aluminum block heater and equipped with triple internal temperature measurement and pressure maintenance. 60 ml of catalyst are installed in each case and the upper part of the reactor tube is filled with porcelain rings. The olefin and amine are fed in from above.
- the analysis of the reactor discharges is carried out by gas chromatography and partly additionally carried out by distillation.
- Catalyst D is obtained by treating 50 g of catalyst A with 250 ml of 15% hydrochloric acid under reflux for 1 h, washing Cl-free after filtration, drying at 110 ° C./16 h and calcining at 500 ° C./5 h.
- Catalyst E is prepared by impregnating 50 g of catalyst A with 9.4 g of Zn (NO 3 ) 3 .6H 2 O and subsequent calcination at 540 ° C / 2h.
- Catalyst G is obtained by forming the borosilicate zeolite described in Example 1 into strands with a mixture of 90% by weight of highly disperse SiO 2 and 10% by weight of boehmite in a weight ratio of 60:40, drying at 110 ° C./16 h and at 500 ° C / 16 h is calcined.
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Aminen durch Anlagerung von Ammoniak oder analog reagierenden Aminen an Olefine.The invention relates to a process for the preparation of amines by addition of ammonia or analogous amines to olefins.
Bei der Addition von Ammoniak oder analog reagierenden Aminen an Olefine handelt es sich um eine seit langem bekannte und vielfach beschriebene Reaktion. Eine technische Realisierung ist bislang nicht erfolgt, da nach den bekannten Verfahren nur ungenügende Selektivitäten und/oder Katalysator-Standzeiten erreicht werden, wie beispielsweise nach US-PS 2 623 061, US-PS 2 422 631, US-PS 2 501 556 und US-PS 3 412 158. Auch das in US-PS 4 307 250 beschriebene Verfahren eignet sich nicht für die Durchführung im technischen Maßstab. Die als Katalysator verwendeten Alumino-Zeolithe begünstigen starke Polymerbildung und nachfolgende Verkokung, die d.en Katalysator schnell desaktiviert.The addition of ammonia or analogous amines to olefins is a reaction which has been known for a long time and has been described many times. A technical implementation has not yet taken place, since only insufficient selectivities and / or catalyst service lives are achieved by the known processes, such as, for example, according to US Pat. No. 2,623,061, US Pat. No. 2,422,631, US Pat PS 3 412 158. The method described in US Pat. No. 4,307,250 is also unsuitable for implementation on an industrial scale. The alumino zeolites used as a catalyst promote strong polymer formation and subsequent coking, which quickly deactivates the catalyst.
Es wurde nun gefunden, daß man hohe Standzeiten und hohe Selektivität der Katalysatoren bei der Herstellung von Aminen aus Olefinen und Ammoniak oder primären oder sekundären Aminen bei Temperaturen zwischen 80°C und 400°C und bei Drücken zwischen 40 und 700 bar in Gegenwart eines zeolithischen Katalystors erzielt, wenn man Olefin und Ammoniak oder primäre oder sekundäre Amine oder Gemische derselben in Gegenwart eines Borosilikat-oder Borogermanatzeolithen des Pentasil-Typs als Katalysator umsetzt, das erhaltene Amin abtrennt und die nichtumgesetzten Einsatzstoffe zurückführt.It has now been found that long service lives and high selectivity of the catalysts in the preparation of amines from olefins and ammonia or primary or secondary amines at temperatures between 80 ° C and 400 ° C and at pressures between 40 and 700 bar in the presence of a zeolitic Catalysts are achieved if olefin and ammonia or primary or secondary amines or mixtures thereof are reacted in the presence of a borosilicate or borogermanate zeolite of the pentasil type as a catalyst, the amine obtained is separated off and the unreacted starting materials are recycled.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, daß bereits mit niedrigem Ammoniak- bzw. Amin-Uberschuß eine hohe Selektivität an gewünschtem Reaktionsprodukt erzielt und die Dimerisierung und/oder Oligomerisierung des eingesetzten Olefins vermieden wird.The process according to the invention is characterized in that a high selectivity of the desired reaction product is achieved even with a low excess of ammonia or amine and the dimerization and / or oligomerization of the olefin used is avoided.
Eine Ausführungsform dieses Verfahrens besteht darin, daß man Ammoniak und/oder Amine zusammen mit Olefinen im molaren Verhältnis von 1:1 bis 5:1 gemischt einem Festbett- oder Wirbelbettreaktor zuführt und bei einem Druck von 40 bis 700 bar, insbesondere 200 bis 300 bar und einer Temperatur von 80 bis 400°C, insbesondere von 250 bis 350°C in der Gasphase oder im überkritischen Zustand umsetzt. Eine andere Ausführungsform besteht darin, daß die Reaktion in Flüssigphase bei einem Druck von 40 bis 80 bar und einer Temperatur von 60°C bis 120°C in einem Rührkessel, einem Fest-/ Flüssigkeit-Fließbett oder einem Strömungsrohr durchgeführt wird.One embodiment of this process consists in that ammonia and / or amines are mixed together with olefins in a molar ratio of 1: 1 to 5: 1 and fed to a fixed bed or fluidized bed reactor and at a pressure of 40 to 700 bar, in particular 200 to 300 bar and a temperature of 80 to 400 ° C, in particular from 250 to 350 ° C in the gas phase or in the supercritical state. Another embodiment is that the reaction in the liquid phase is carried out at a pressure of 40 to 80 bar and a temperature of 60 ° C to 120 ° C in a stirred tank, a solid / liquid fluidized bed or a flow tube.
Aus dem Reaktionsaustrag wird das gewünschte Produkt mit Hilfe bekannter Methoden, beispielsweise Destillation oder Extraktion, erhalten und nötigenfalls mittels weiterer Trennoperationen auf die gewünschte Reinheit gebracht. Die nichtumgesetzten Eingangsstoffe werden in den Reaktor zurückgeführt.The desired product is obtained from the reaction discharge using known methods, for example distillation or extraction, and If necessary, brought to the desired purity by means of further separation operations. The unreacted input materials are returned to the reactor.
Man kann einfach oder mehrfach ungesättigte Olefine mit 2 bis 10 C-Atomen bzw. deren Mischungen als Ausgangsstoffe verwenden. Wegen der geringer ausgeprägten Polymerisationsneigung eignen sich Monoolefine besser als Di- und Polyolefine, doch können diese mit Hilfe höherer Ammoniak- bzw. Aminüberschüsse ebenso selektiv umgesetzt werden. Die Lage des Gleichgewichts und damit der Umsatz zum gewünschten Amin ist sehr stark vom gewählten Reaktionsdruck abhängig. Hoher Druck begünstig das Additionsprodukt, doch stellt im allgemeinen aus technischen und wirtschaftlichen Gründen der Druckbereich bis 300 bar das Optimum dar. Die Selektivität der Reaktion wird - neben Größen wie Ammoniak-/Amin-Uberschuß und Katalysator - in hohem Maß durch die Temperatur beeinflußt. Zwar nimmt die Reaktionsgeschwindigkeit der Additionsreaktion mit steigender Temperatur stark zu, doch werden konkurrierende Crack- und Rekombinationsreaktionen des Oleflns gleichzeitig gefördert. Die Lage des Temperaturoptimums bezüglich Umsatz und Selektivität Ist von der Konstitution des Olefins, des eingesetzten Amins und des Katalysators abhängig und liegt meist im Bereich von 250°C bis 350°C. Die Verweilzeit Ist abhängig von den Einsatzstoffen und liegt zweckmäßigerweise im Bereich zwischen Bruchteilen einer Sekunde und wenigen Minuten.It is possible to use mono- or polyunsaturated olefins with 2 to 10 carbon atoms or mixtures thereof as starting materials. Because of the less pronounced tendency to polymerize, monoolefins are more suitable than di- and polyolefins, but these can also be reacted selectively with the aid of higher excesses of ammonia or amine. The position of the equilibrium and thus the conversion to the desired amine depends very much on the reaction pressure chosen. High pressure favors the addition product, but in general the pressure range up to 300 bar is the optimum for technical and economic reasons. The selectivity of the reaction - in addition to quantities such as excess ammonia / amine and catalyst - is influenced to a high degree by the temperature. Although the reaction rate of the addition reaction increases sharply with increasing temperature, competing cracking and recombination reactions of the olefin are promoted at the same time. The location of the optimum temperature with regard to conversion and selectivity depends on the constitution of the olefin, the amine used and the catalyst and is usually in the range from 250 ° C. to 350 ° C. The dwell time depends on the starting materials and is expediently in the range between fractions of a second and a few minutes.
Als Katalysatoren für die Aminierung von Olefinen verwendet man Borosilikat- oder Borogermanat-Zeolithe des Pentasiltyps.Borosilicate or borogermanate zeolites of the pentasil type are used as catalysts for the amination of olefins.
Geeignete Borosilikatzeolithe bzw. Borogermanatzeolithe werden bei 90 bis 170°C unter autogenem Druck synthetisiert, indem man eine Borverbindung, z.B. H3B03 mit einer Siliciumverbindung oder einer Germaniumverbindung, vorzugsweise hochdisperses Siliciumdioxid und Germaniumoxid in wäßriger Aminlösung, insbesondere in 1,6-Hexandiamin- oder 1,3-Propandiamin- oder Triethylentetramin-Lösung mit und ohne Alkali- oder Erdalkalizusatz zur Reaktion bringt.Suitable borosilicate zeolites or borogermanate zeolites are synthesized at 90 to 170 ° C under autogenous pressure by using a boron compound, for example H 3 B0 3 with a silicon compound or a germanium compound, preferably highly disperse silicon dioxide and germanium oxide in aqueous amine solution, especially in 1,6-hexanediamine - or 1,3-propanediamine or triethylenetetramine solution with and without addition of alkali or alkaline earth metal to react.
Derartige Borosilikatzeolithe oder Borogermanatzeolithe können ebenfalls hergestellt werden, wenn man die Reaktion statt in wäßriger Aminlösung in etherischer Lösung, z.B. Diethylenglykoldimethylether oder in alkoholischer Lösung, z.B. Methanol bzw. 1,4-Butandiol durchführt.Such borosilicate zeolites or borogermanate zeolites can also be prepared if the reaction is carried out in ethereal solution, e.g. Diethylene glycol dimethyl ether or in alcoholic solution, e.g. Performs methanol or 1,4-butanediol.
Die so hergestellten Borosilikatzeolithe und Borogermanatzeolithe kann man nach ihrer Isolierung, Trocknung bei 100 bis 160°C, vorzugsweise bei etwa 110°C und Calcination bei 450 bis 550°C, vorzugsweise bei etwa 500°C, mit einem Bindemittel im Verhältnis 90:10 bis 40:60 Gew.-% zu Strängen oder Tabletten verformen. Als Bindemittel eignen sich verschiedene Aluminiumoxide, bevorzugt Boehmit, amorphe Aluminosilikate mit einem SiO2/Al2O3-Verhältnis von 25:75 bis 95:5, Siliciumdioxid, bevorzugt hochdisperses Si02, Gemische aus hochdispersem Si02 und hochdispersem A1203, hochdisperses TiO2 sowie Ton. Nach der Verformung werden die Extrudate oder Presslinge zweckmäßig bei 110°C/16 h getrocknet und bei 500°C/16 h calciniert.The borosilicate zeolites and borogermanate zeolites thus produced can be isolated after their isolation, drying at 100 to 160 ° C, preferably at about 110 ° C and calcination at 450 to 550 ° C, preferably at about 500 ° C, with a binder in a ratio of 90:10 to 40:60 wt .-% to form strands or tablets. Various aluminum oxides, preferably boehmite, amorphous aluminosilicates with an SiO 2 / Al 2 O 3 ratio of 25:75 to 95: 5, silicon dioxide, preferably highly disperse Si0 2 , mixtures of highly disperse Si0 2 and highly disperse A1 2 0 3 are suitable as binders , highly disperse TiO 2 and clay. After the shaping, the extrudates or compacts are expediently dried at 110 ° C./16 h and calcined at 500 ° C./16 h.
Eine besondere Ausführungsform besteht darin, daß der isolierte Borosillkat- und/oder Borogermantzeolith direkt nach der Trocknung verformt wird und erstmals nach der Verformung einer Caleination unterworfen wird.A special embodiment consists in that the isolated borosillate and / or borogermantzeolite is deformed immediately after drying and is subjected to a caleination for the first time after the deformation.
Aus dem zu Strängen verformten Katalysator kann man durch Mahlen und Sieben Wirbelgut in der Größe von 0,1 bis 0,8 mm erhalten.From the catalyst, which has been shaped into strands, it is possible to obtain fluidized material in the size of 0.1 to 0.8 mm by grinding and sieving.
Nach Desaktivierung der zeolithischen Katalysatoren durch Koksabscheidung während der erfindungsgemäßen Umsetzung kann man die Katalysatoren durch Abbrennen der Koksablagerung mit Luft oder mit einem Luft/N2-Gemisch bei 400°C bis 550°C, bevorzugt bei etwa 500°C, in einfacher Weise regenerieren. Sie erhalten dadurch ihre Anfangsaktivität zurück.After deactivation of the zeolitic catalysts by coke separation during the reaction according to the invention, the catalysts can be regenerated in a simple manner by burning off the coke deposit with air or with an air / N 2 mixture at 400 ° C. to 550 ° C., preferably at about 500 ° C. . This gives you back your initial activity.
Zur Erhöhung der Selektivität, der Standzeit und der Anzahl der möglichen Regenerierungen kann man verschiedene Modifizierungen an zeolithischen Katalysatoren vornehmen.To increase the selectivity, the service life and the number of possible regenerations, various modifications can be made to zeolitic catalysts.
Eine Modifizierung der Katalysatoren besteht darin, daß man die unverformten oder die verformten Zeolithe mit Alkalimetallen wie Na und K, Erdalkalimetallen wie Ca, Mg, Erdmetallen wie Tl, Ubergangsmetallen wie Mn, Fe, Mo, Cu, Zn und seltene Erdmetalle wie La,_Ce ionenauschen bzw. dotieren kann.A modification of the catalysts is that the undeformed or the deformed zeolites with alkali metals such as Na and K, alkaline earth metals such as Ca, Mg, earth metals such as Tl, transition metals such as Mn, Fe, Mo, Cu, Zn and rare earth metals such as La, _Ce ion noise or doping.
Eine vorteilhafte Ausführungsform besteht darin, daß man die verformten Pentasilzeolithe in einem Strömungsrohr vorlegt und bei 20 bis 100°C, z.B. ein Halogenid oder ein Nitrat der oben beschriebenen Metalle darüberleitet. Ein derartiger Ionenaustausch kann z.B. an der Wasserstoff-, Ammonium- und Alkaliform der Zeolithe vorgenommen werden.An advantageous embodiment is that the deformed pentasil zeolites are placed in a flow tube and at 20 to 100 ° C, e.g. a halide or a nitrate of the metals described above passes over it. Such ion exchange can e.g. on the hydrogen, ammonium and alkali form of the zeolites.
Eine andere Möglichkeit der Metallaufbringung auf die Zeolithe besteht darin, daß man das zeolithische Material, z.B. mit einem Halogenid, einem Nitrat oder einem Oxid der oben beschriebenen Metalle in wäßriger oder alkoholischer Lösung imprägniert.Another way of applying metal to the zeolites is to use the zeolitic material, e.g. impregnated with a halide, a nitrate or an oxide of the metals described above in aqueous or alcoholic solution.
Sowohl an einen Ionenaustausch als auch an eine Imprägnierung kann man eine Trocknung, wahlweise eine abermalige Calcination anschließen. Bei metalldotierten Zeolithen kann eine Nachbehandlung mit Wasserstoff und/ oder mit Wasserdampf günstig sein.Both ion exchange and impregnation can be followed by drying or, alternatively, repeated calcination. In the case of metal-doped zeolites, post-treatment with hydrogen and / or with water vapor can be advantageous.
Eine weitere Möglichkeit der Modifizierung besteht darin, daß man das zeolithische Material - verformt oder unverformt - einer Behandlung mit Säuren, wie Salzsäure-, Flußsäure- und Phosphorsäure unterwirft.Another possibility for modification consists in subjecting the zeolitic material - deformed or undeformed - to treatment with acids such as hydrochloric, hydrofluoric and phosphoric acids.
Eine besondere Ausführungsform besteht darin, daß man das zeolithische Pulver vor seiner Verformung mit Flußsäure 0,001 n bis 2 n, bevorzugt 0,05 bis 0,5 n 1 bis 3 Stunden unter Rückfluß behandelt. Nach Abfiltrieren und Auswaschen wird bei 100 bis 160°C getrocknet und bei 400 bis 550°C calciniert. Eine weitere besondere Ausführungsform liegt in einer HCl-Behandlung der Zeolithe nach ihrer Verformung mit Bindemittel. Hierbei wird der Zeolith 1 bis 3 Stunden zwischen 60 und 80°C mit einer 3 bis 25%igen, insbesondere mit einer 12 bis 20%igen Salzsäure behandelt, anschließend ausgewaschen, bei 100 bis 160°C getrocknet und bei 400 bis 550°C calciniert.A special embodiment consists in treating the zeolitic powder under reflux with hydrofluoric acid 0.001 n to 2 n, preferably 0.05 to 0.5 n, for 1 to 3 hours before it is shaped. After filtering off and washing out, it is dried at 100 to 160 ° C. and calcined at 400 to 550 ° C. Another special embodiment is an HCl treatment of the zeolites after they have been deformed with a binder. Here, the zeolite is treated for 1 to 3 hours between 60 and 80 ° C with a 3 to 25%, in particular with a 12 to 20% hydrochloric acid, then washed out, dried at 100 to 160 ° C and at 400 to 550 ° C calcined.
Eine andere Möglichkeit der Modifizierung ist gegeben durch einen Austausch mit Ammonsalzen, z.B. mit NH4Cl oder mit Mono-, Di- oder Polyaminen. Hierbei wird der in der H-Form oder einer anderen Ammoniumform vorliegende, mit Bindemittel verformte Zeolith bei 60 bis 80°C mit 10 bis 25%iger, bevorzugt 20%iger NH4Cl-Lösung 2 h kontinuierlich in gewichtsmäßiger Zeolith/Ammonchlorid-Lösung von 1:15 ausgetauscht und danach bei 100 bis 120°C getrocknet.Another possibility for modification is given by an exchange with ammonium salts, for example with NH 4 Cl or with mono-, di- or polyamines. Here, the zeolite, which is present in the H form or another ammonium form and deformed with binder, is continuously at 60 to 80 ° C. with 10 to 25%, preferably 20%, NH 4 Cl solution in a weight-based zeolite / ammonium chloride solution exchanged by 1:15 and then dried at 100 to 120 ° C.
Die Katalysatoren kann man als 2 mm bis 4 mm Stränge, als Tabletten mit 3 bis 5 mm Durchmesser oder als Wirbelgut mit einer Größe von 0,1 bis 0,8 mm oder als Split mit 0,5- 1 mm Durchmesser für die Aminierung der Olefine einsetzen.The catalysts can be used as 2 mm to 4 mm strands, as tablets with 3 to 5 mm diameter or as fluidized material with a size of 0.1 to 0.8 mm or as split with 0.5-1 mm diameter for the amination of the Use olefins.
Die nachfolgenden Beispiele veranschaulichen die Erfindung.The following examples illustrate the invention.
Katalysator A wird in einer hydrothermalen Synthese aus 64 g Si02 (hochdisperse Kieselsäure) 12,2 g H3BO3, 800 g einer wäßrigen 1,6-Hexandiamin--Lösung (Mischung 50:50 Gew.-%) bei 170°C unter autogenem Druck in einem Rührautoklaven hergestellt. Nach Abfiltrieren und Auswaschen wird das kristalline Reaktionsprodukt bei 110°C/24 h getrocknet und bei 500°C/24 h calciniert. Man erhalt einen Borosilikatzeolithen vom Pentasiltyp, der 94,2 Gew.-% Si02 und 2,32 Gew.-% B203 enthält.Catalyst A is in a hydrothermal synthesis from 64 g Si0 2 (highly disperse silica) 12.2 g H 3 BO 3 , 800 g of an aqueous 1,6-hexanediamine solution (mixture 50:50 wt .-%) at 170 ° C produced under autogenous pressure in a stirred autoclave. After filtering off and washing out, the crystalline reaction product is dried at 110 ° C./24 h and at 500 ° C./24 h calcined. A pentasil type borosilicate zeolite is obtained which contains 94.2% by weight of SiO 2 and 2.32% by weight of B 2 0 3 .
Aus diesem Zeolith werden durch Verformen mit Boehmit im Gewichtsverhältnis 60:40 2 mm-Stränge hergestellt, die bei 110°C/16 h getrocknet und bei 500°C/24 h calciniert werden.2 mm strands are produced from this zeolite by shaping with boehmite in a weight ratio of 60:40, which are dried at 110 ° C./16 h and calcined at 500 ° C./24 h.
Katalysator B wird durch Behandlung von 50 g des oben beschriebenen Borosilikatzeolithen mit 140 ml O,ln HF unter Rückfluß während 1 h hergestellt. Nach der Filtration und Auswaschen mit Wasser wird bei 110°C/16 h getrocknet und bei 500°C/5 h calciniert. Dieses Produkt wird mit Boehmit im Verhältnis 60:40 verstrangt, bei 110°C/16 h getrocknet und bei 500°C/16 h calciniert.Catalyst B is prepared by treating 50 g of the borosilicate zeolite described above with 140 ml of O, lN HF under reflux for 1 h. After filtration and washing with water, the mixture is dried at 110 ° C./16 h and calcined at 500 ° C./5 h. This product is extruded with boehmite in a ratio of 60:40, dried at 110 ° C./16 h and calcined at 500 ° C./16 h.
Katalysator C wird erhalten, indem am Katalysator A ein Ionenaustausch mit einer Na-Verbindung bei RT vorgenommen wird, so daß der Katalysator nach Auswaschen mit Wasser und Trocknung bei 110°C/16 h einen Na-Gehalt von 0,32 Gew.-% aufweist.Catalyst C is obtained by carrying out an ion exchange with a Na compound at RT on catalyst A, so that the catalyst, after washing out with water and drying at 110 ° C./16 h, has a Na content of 0.32% by weight. having.
In einen 0,3 1-Rührautoklaven werden jeweils 10 ml der oben beschriebenen Katalysatoren A, B oder C gegeben und nach dem Verschließen die Olefine und Ammoniak bzw. Amine aufgedrückt. Die Menge an Einsatzprodukt wird so bemessen, daß bei der gewählten Reaktionstemperatur der gewünschte Druck als Eigendruck der Reaktionspartner erreicht wird. Das molare Verhältnis von Ammoniak/Amin zu Olefin wird von 1:1 bis 5:1 variiert, die Reaktionsdauer auf 30 min. festgelegt.10 ml each of the catalysts A, B or C described above are placed in a 0.3 l stirred autoclave and, after sealing, the olefins and ammonia or amines are pressed on. The amount of product used is such that the desired pressure is reached as the intrinsic pressure of the reactants at the selected reaction temperature. The molar ratio of ammonia / amine to olefin is varied from 1: 1 to 5: 1, the reaction time to 30 min. fixed.
Der Austrag wurde getrennt nach Flüssig- und Gasphase gaschromatographisch untersucht. Die in Tabelle 1 aufgeführten Umsätze beziehen sich immer auf das Olefin; die angegebenen Selektivitäten beziehen sich auf die Hauptprodukte: Ethylamin aus Ethylen, Isopropylamin aus Propylen, Isobutylamin aus Buten-1, tertiär Butylamin aus Isobuten, Isopentylamin aus Isobuten mit Methylamin und 1-Amino-4(1-aminoethyl)cyclohexan aus 4-Vinyl-l-cyclohexen.
Für eine kontinuierliche Herstellung wird ein Hochdruck-Reaktor mit 2 m Länge und 24 mm Innendurchmesser eingesetzt, der mittels einer Alublockheizung beheizt und mit dreifacher Innentemperaturmessung sowie mit einer Druckhaltung ausgestattet ist. Es werden jeweils 60 ml Katalysator eingebaut und der obere Teil des Reaktorrohres mit Porzellanringen gefüllt. Der Zulauf von Olefin und Amin erfolgt von oben.For a continuous production, a high-pressure reactor with a length of 2 m and an inner diameter of 24 mm is used, which is heated by an aluminum block heater and equipped with triple internal temperature measurement and pressure maintenance. 60 ml of catalyst are installed in each case and the upper part of the reactor tube is filled with porcelain rings. The olefin and amine are fed in from above.
Die Analyse der Reaktorausträge wird gaschromatographisch und z.T. zusätzlich destillativ durchgeführt.The analysis of the reactor discharges is carried out by gas chromatography and partly additionally carried out by distillation.
Die Ergebnisse mit den verschiedenen Katalysatoren sind in Tabelle 2 wiedergegeben. Einige Ergebnisse wurden ohne zwischenzeitliche Regenerierung des Katalysators erhalten. Die Analyse des nach 28 Tagen ununterbrochener Betriebsdauer ausgebauten Katalysators ergibt einen Kohlenstoffgehalt von 11,0 %.
Katalysator D wird erhalten, indem man 50 g des Katalysators A mit 250 ml 15%iger Salzsäure unter Rückfluß 1 h behandelt, nach der Filtration Cl-frei wäscht, bei 110°C/16 h trocknet und bei 500°C/5h calciniert.Catalyst D is obtained by treating 50 g of catalyst A with 250 ml of 15% hydrochloric acid under reflux for 1 h, washing Cl-free after filtration, drying at 110 ° C./16 h and calcining at 500 ° C./5 h.
Katalysator E wird durch Imprägnierung von 50 g des Katalysators A mit 9,4 g Zn(NO3)3.6H2O und anschließender Calcination bei 540°C/2h hergestellt.Catalyst E is prepared by impregnating 50 g of catalyst A with 9.4 g of Zn (NO 3 ) 3 .6H 2 O and subsequent calcination at 540 ° C / 2h.
Katalysator F erhält man, indem der in Beispiel 1 beschriebene Borosilikatzeolith mit einem Gemisch aus hochdispersem Si02 und A1203 (Al203-Gehalt = 3,5 Gew.%) im Gewichtsverhältnis 60:40 zu Strängen verformt, bei 110°C/16 h getrocknet und bei 500°C/16 h calciniert wird.Catalyst F is obtained by stripping the borosilicate zeolite described in Example 1 with a mixture of highly disperse Si0 2 and A1 2 0 3 (Al 2 0 3 content = 3.5% by weight) in a weight ratio of 60:40, at 110 ° C / 16 h and calcined at 500 ° C / 16 h.
Katalysator G erhält man, indem der in Beispiel 1 beschriebene Borosilikatzeolith mit einem Gemisch aus 90 Gew.% hochdispersem Si02 und 10 Gew.% Boehmit im Gewichtsverhältnis 60:40 zu Strängen verformt, bei 110°C/16 h getrocknet und bei 500°C/16 h calciniert wird.Catalyst G is obtained by forming the borosilicate zeolite described in Example 1 into strands with a mixture of 90% by weight of highly disperse SiO 2 and 10% by weight of boehmite in a weight ratio of 60:40, drying at 110 ° C./16 h and at 500 ° C / 16 h is calcined.
In einem Rohrreaktor (6 mm Innendurchmesser) wird unter isothermen Bedingungen bei 300°C und einem Druck von 300 bar ein Gemisch aus Isobuten und Ammoniak im molaren Verhältnis von 1:1,3 an den Katalysatoren A, B, C, D, E, F und G diskontinuierlich umgesetzt. Die Reaktionsprodukte werden im Gaschromatographen analysiert.A mixture of isobutene and ammonia in a molar ratio of 1: 1.3 over the catalysts A, B, C, D, E, is in a tube reactor (6 mm inner diameter) under isothermal conditions at 300 ° C and a pressure of 300 bar. F and G implemented discontinuously. The reaction products are analyzed in a gas chromatograph.
Die Versuchsergebnisse sind in Tabelle 3 zusammengefaßt.
Claims (7)
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AT84108454T ATE23327T1 (en) | 1983-07-27 | 1984-07-18 | PROCESSES FOR PRODUCTION OF AMINES. |
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DE19833327000 DE3327000A1 (en) | 1983-07-27 | 1983-07-27 | METHOD FOR PRODUCING AMINES |
DE3327000 | 1983-07-27 |
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EP0133938A2 true EP0133938A2 (en) | 1985-03-13 |
EP0133938A3 EP0133938A3 (en) | 1985-04-17 |
EP0133938B1 EP0133938B1 (en) | 1986-11-05 |
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EP84108454A Expired EP0133938B1 (en) | 1983-07-27 | 1984-07-18 | Process for preparing amines |
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EP (1) | EP0133938B1 (en) |
JP (1) | JPS6084246A (en) |
AT (1) | ATE23327T1 (en) |
CA (1) | CA1216596A (en) |
DE (2) | DE3327000A1 (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0186395A2 (en) * | 1984-12-24 | 1986-07-02 | Mobil Oil Corporation | Zeolite catalyst composition having improved stability |
EP0198437A2 (en) * | 1985-04-16 | 1986-10-22 | BASF Aktiengesellschaft | Crystalline zeolite borosilicate catalysts, process for their preparation and their use |
EP0263462A2 (en) * | 1986-10-08 | 1988-04-13 | BASF Aktiengesellschaft | Process for the manufacture of amines |
EP0296495A2 (en) * | 1987-06-23 | 1988-12-28 | BASF Aktiengesellschaft | Process for the preparation of diamines |
EP0431451A2 (en) * | 1989-12-06 | 1991-06-12 | BASF Aktiengesellschaft | Process for the preparation of amines |
EP0469719A1 (en) * | 1990-08-01 | 1992-02-05 | Huntsman Corporation | Alkylamine synthesis over montmorillonite clays |
EP0699653A1 (en) * | 1994-09-01 | 1996-03-06 | BASF Aktiengesellschaft | Method for the preparation of amines |
WO1997007088A1 (en) * | 1995-08-17 | 1997-02-27 | Basf Aktiengesellschaft | METHOD OF PREPARING AMINES FROM OLEFINS OVER BORON β-ZEOLITES |
EP0778259A2 (en) | 1995-12-08 | 1997-06-11 | Basf Aktiengesellschaft | Process for the preparation of amines from olefines using SSZ-37 zeolithes |
EP0785185A1 (en) | 1996-01-17 | 1997-07-23 | Basf Aktiengesellschaft | Process for the preparation of amines from olefins with crystalline oxides based on aluminophosphates having the structure of faujasite |
EP0786449A1 (en) | 1996-01-26 | 1997-07-30 | Basf Aktiengesellschaft | Process for the preparation of amines from olefins on hexagonal faujasites |
US5763668A (en) * | 1995-07-04 | 1998-06-09 | Basf Aktiengesellschaft | Process for aminating a mixture obtained in cracking a mineral oil fraction with ammonia or a primary or secondary amine over specific heterogeneous catalysts |
US5780680A (en) * | 1996-04-19 | 1998-07-14 | Basf Aktiengesellschaft | Preparation of amines from olefins over mesoporous oxides having a high surface area |
US5840988A (en) * | 1996-12-03 | 1998-11-24 | Basf Aktiengesellschaft | Preparation of amines from olefins on zeolites of the MCM-49 or MCM-56 type |
US5874621A (en) * | 1997-02-25 | 1999-02-23 | Basf Aktiengesellschaft | Preparation of amines from olefins over NU-85 zeolites |
US5877352A (en) * | 1996-12-03 | 1999-03-02 | Basf Aktiengesellschaft | Preparation of amines from olefins on boron-MCM-22 or ERB-1 zeolites |
US5886226A (en) * | 1995-12-08 | 1999-03-23 | Basf Aktiengesellschaft | Process for producing amines from olefins on zeolites of types SSZ-33, CIT-1 or mixtures thereof |
US5900508A (en) * | 1995-07-20 | 1999-05-04 | Basf Aktiengesellschaft | Preparation of amines from olefins over zeolites of the type PSH-3, MCM-22, SSZ-25 or mixtures thereof |
WO2001085667A1 (en) | 2000-05-12 | 2001-11-15 | Duslo, A.S. Šal'a | Process of preparation of aliphatic amines |
US6350914B1 (en) | 1996-07-30 | 2002-02-26 | Basf Aktiengesellschaft | Preparation of amines from olefins over zeolites having an NES structure |
EP1462165A1 (en) * | 2003-03-27 | 2004-09-29 | Basf Aktiengesellschaft | Method for the production of alkylamines and for increasing the hydroamination activity of calcined zeolitic catalysts |
WO2009124924A1 (en) * | 2008-04-09 | 2009-10-15 | Basf Se | Method for pre-treating hydroamination catalysts |
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DE3721777A1 (en) * | 1987-07-01 | 1989-01-12 | Basf Ag | METHOD FOR PRODUCING N-HETEROCYCLES |
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CZ302341B6 (en) * | 2000-05-12 | 2011-03-23 | Duslo A. S. | Process for preparing aliphatic amines |
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- 1983-07-27 DE DE19833327000 patent/DE3327000A1/en not_active Withdrawn
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- 1984-07-18 AT AT84108454T patent/ATE23327T1/en not_active IP Right Cessation
- 1984-07-18 EP EP84108454A patent/EP0133938B1/en not_active Expired
- 1984-07-18 DE DE8484108454T patent/DE3461181D1/en not_active Expired
- 1984-07-23 CA CA000459485A patent/CA1216596A/en not_active Expired
- 1984-07-25 JP JP59153304A patent/JPS6084246A/en active Pending
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Cited By (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0186395A2 (en) * | 1984-12-24 | 1986-07-02 | Mobil Oil Corporation | Zeolite catalyst composition having improved stability |
EP0186395A3 (en) * | 1984-12-24 | 1987-06-10 | Mobil Oil Corporation | Zeolite catalyst composition having improved stability |
EP0198437A2 (en) * | 1985-04-16 | 1986-10-22 | BASF Aktiengesellschaft | Crystalline zeolite borosilicate catalysts, process for their preparation and their use |
EP0198437A3 (en) * | 1985-04-16 | 1987-08-26 | Basf Aktiengesellschaft | Crystalline zeolite borosilicate catalysts, process for their preparation and their use |
EP0263462A3 (en) * | 1986-10-08 | 1989-07-26 | Basf Aktiengesellschaft | Process for the manufacture of amines |
EP0263462A2 (en) * | 1986-10-08 | 1988-04-13 | BASF Aktiengesellschaft | Process for the manufacture of amines |
EP0296495A2 (en) * | 1987-06-23 | 1988-12-28 | BASF Aktiengesellschaft | Process for the preparation of diamines |
EP0296495A3 (en) * | 1987-06-23 | 1989-12-20 | Basf Aktiengesellschaft | Process for the preparation of diamines |
EP0431451A2 (en) * | 1989-12-06 | 1991-06-12 | BASF Aktiengesellschaft | Process for the preparation of amines |
EP0431451A3 (en) * | 1989-12-06 | 1991-11-06 | Basf Aktiengesellschaft | Process for the preparation of amines |
EP0469719A1 (en) * | 1990-08-01 | 1992-02-05 | Huntsman Corporation | Alkylamine synthesis over montmorillonite clays |
EP0699653A1 (en) * | 1994-09-01 | 1996-03-06 | BASF Aktiengesellschaft | Method for the preparation of amines |
US5763668A (en) * | 1995-07-04 | 1998-06-09 | Basf Aktiengesellschaft | Process for aminating a mixture obtained in cracking a mineral oil fraction with ammonia or a primary or secondary amine over specific heterogeneous catalysts |
US5900508A (en) * | 1995-07-20 | 1999-05-04 | Basf Aktiengesellschaft | Preparation of amines from olefins over zeolites of the type PSH-3, MCM-22, SSZ-25 or mixtures thereof |
WO1997007088A1 (en) * | 1995-08-17 | 1997-02-27 | Basf Aktiengesellschaft | METHOD OF PREPARING AMINES FROM OLEFINS OVER BORON β-ZEOLITES |
US5739405A (en) * | 1995-12-08 | 1998-04-14 | Basf Aktiengesellschaft | Preparation of amines from olefins over zeolites of the type SSZ-37 |
US5886226A (en) * | 1995-12-08 | 1999-03-23 | Basf Aktiengesellschaft | Process for producing amines from olefins on zeolites of types SSZ-33, CIT-1 or mixtures thereof |
EP0778259A2 (en) | 1995-12-08 | 1997-06-11 | Basf Aktiengesellschaft | Process for the preparation of amines from olefines using SSZ-37 zeolithes |
US5786510A (en) * | 1996-01-17 | 1998-07-28 | Basf Aktiengesellschaft | Preparation of amines from olefins over crystalline oxides based on aluminum phosphates and having faujasite structure |
EP0785185A1 (en) | 1996-01-17 | 1997-07-23 | Basf Aktiengesellschaft | Process for the preparation of amines from olefins with crystalline oxides based on aluminophosphates having the structure of faujasite |
EP0786449A1 (en) | 1996-01-26 | 1997-07-30 | Basf Aktiengesellschaft | Process for the preparation of amines from olefins on hexagonal faujasites |
US5773660A (en) * | 1996-01-26 | 1998-06-30 | Basf Aktiengesellschaft | Preparation of amines from olefins over hexagonal faujasites |
US5780680A (en) * | 1996-04-19 | 1998-07-14 | Basf Aktiengesellschaft | Preparation of amines from olefins over mesoporous oxides having a high surface area |
US6350914B1 (en) | 1996-07-30 | 2002-02-26 | Basf Aktiengesellschaft | Preparation of amines from olefins over zeolites having an NES structure |
US5840988A (en) * | 1996-12-03 | 1998-11-24 | Basf Aktiengesellschaft | Preparation of amines from olefins on zeolites of the MCM-49 or MCM-56 type |
US5877352A (en) * | 1996-12-03 | 1999-03-02 | Basf Aktiengesellschaft | Preparation of amines from olefins on boron-MCM-22 or ERB-1 zeolites |
US5874621A (en) * | 1997-02-25 | 1999-02-23 | Basf Aktiengesellschaft | Preparation of amines from olefins over NU-85 zeolites |
WO2001085667A1 (en) | 2000-05-12 | 2001-11-15 | Duslo, A.S. Šal'a | Process of preparation of aliphatic amines |
EP1462165A1 (en) * | 2003-03-27 | 2004-09-29 | Basf Aktiengesellschaft | Method for the production of alkylamines and for increasing the hydroamination activity of calcined zeolitic catalysts |
US7074964B2 (en) | 2003-03-27 | 2006-07-11 | Basf Aktiengesellschaft | Preparation of alkylamines and method of increasing the hydroamination activity of calcined zeolitic catalysts |
CN1312110C (en) * | 2003-03-27 | 2007-04-25 | 巴斯福股份公司 | Preparation method of alkylamine and method of increasing hydroamination activity of calicining zeolite catalyst |
WO2009124924A1 (en) * | 2008-04-09 | 2009-10-15 | Basf Se | Method for pre-treating hydroamination catalysts |
US8779205B2 (en) | 2008-04-09 | 2014-07-15 | Basf Se | Method for pre-treating hydroamination catalysts |
Also Published As
Publication number | Publication date |
---|---|
ATE23327T1 (en) | 1986-11-15 |
JPS6084246A (en) | 1985-05-13 |
DE3327000A1 (en) | 1985-02-07 |
DE3461181D1 (en) | 1986-12-11 |
CA1216596A (en) | 1987-01-13 |
EP0133938A3 (en) | 1985-04-17 |
EP0133938B1 (en) | 1986-11-05 |
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